CN102617133B - Thermal sensitive ceramic material and high-voltage-resistant thermistor prepared by using thermal sensitive ceramic material and preparation method - Google Patents

Thermal sensitive ceramic material and high-voltage-resistant thermistor prepared by using thermal sensitive ceramic material and preparation method Download PDF

Info

Publication number
CN102617133B
CN102617133B CN 201210080495 CN201210080495A CN102617133B CN 102617133 B CN102617133 B CN 102617133B CN 201210080495 CN201210080495 CN 201210080495 CN 201210080495 A CN201210080495 A CN 201210080495A CN 102617133 B CN102617133 B CN 102617133B
Authority
CN
China
Prior art keywords
parts
sintering
ceramic material
thermal sensitive
sensitive ceramic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN 201210080495
Other languages
Chinese (zh)
Other versions
CN102617133A (en
Inventor
石永丰
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jiangsu Xinlingzhi Electronic Technology Co., Ltd.
Original Assignee
CHANGSHU LINZHI ELECTRONICS Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by CHANGSHU LINZHI ELECTRONICS Co Ltd filed Critical CHANGSHU LINZHI ELECTRONICS Co Ltd
Priority to CN 201210080495 priority Critical patent/CN102617133B/en
Publication of CN102617133A publication Critical patent/CN102617133A/en
Application granted granted Critical
Publication of CN102617133B publication Critical patent/CN102617133B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Abstract

The invention discloses a thermal sensitive ceramic material which comprises the following components in parts by mole: 86.2-87.2 parts of BaCO3, 3.5-4.5 parts of SrCO3, 3.8-4.8 parts of PbO, 5.5-6.5 parts of CaCO3, 101-101.5 parts of TiO2, 0.1-0.15 parts of Y2O3, 0.03-0.04 part of Sb2O3, 0.06-0.08 part of Mn(NO3)2 as well as a sintered liquid phase additive. The invention also discloses a high-voltage-resistant PTC (positive temperature coefficient) thermistor prepared by using the thermal sensitive ceramic material and a preparation method of the PTC thermistor. The method comprises the following steps: mixing the components according to the designed ratio, ball milling by a wet method, pre-sintering, ball milling by a secondary wet method, pelleting and tabletting, sintering and post processing, thereby preparing the PTC thermistor. Through various tests, the PTC thermistor can resist a 10/700 mu S lightening stroke wave of 4KV, and can be applied to systems such as large instruments, devices, electric power.

Description

Thermal sensitive ceramic material and by its high voltage withstanding thermistor and manufacture method that makes
Technical field
The invention belongs to the semiconductor ceramic material field, be specifically related to a kind of thermal sensitive ceramic material, and by this thermal sensitive ceramic material high voltage withstanding thermistor that makes and the method for making this thermistor.
Background technology
Along with the progress of Fibre Optical Communication Technology, need a kind of high voltage withstanding PTC (Positive Temperature Coefficient, posistor) as the protection of telecommunication voice ply-yarn drill, it must reach following performance index:
1, PTC itself can tolerate 4KV, and 10/700uS/40 Ω impacts 10 times, pitch time 60S, PTC can not produce flashover arcing or sliver;
2,4KV, under the 10/700uS/40 Ω impact condition, the maximum loop electric current is less than 60Ap, i.e. equivalent resistance minimum value R under the voltage-sensitive effect of PTC MinAbout 22 Ω;
3, the power induction under 600VAC/600 Ω/1S condition test is 5 times, pitch time 60S;
4, conventional 265V AC power line lapping test;
5, above-mentioned all test events, after test, the resistance varying-ratio of PTC cooling after 1 hour is less than ± 15%, and absolute error is less than 2 Ω;
6, the PTC main electrical parameters is:
A) R25 normal temperature resistance 55 ± 15% Ω
B) V Max＞265VAC (directly loading)
C) diameter 8.0～8.8mm
D) thickness 3.0～3.3mm
E) draw stitch spacing 5.00mm
The communications protection product of market can't satisfy above 6 kinds of requirements simultaneously at present.
Summary of the invention
The high voltage withstanding PTC that the technical problem that the present invention mainly solves provides a kind of thermal sensitive ceramic material and made by this thermal sensitive ceramic material.
The present invention also provides a kind of method of making this PTC.
The technical scheme that the present invention adopts is: a kind of thermal sensitive ceramic material comprises by its composition of mole umber: 86.2～87.2 parts of BaCO 3, 3.5～4.5 parts of SrCO 3, 3.8～4.8 parts of PbO, 5.5～6.5 parts of CaCO 3, 101～101.5 parts of TiO 2, 0.1～0.15 part of Y 2O 3, 0.03～0.04 part of Sb 2O 3, 0.06～0.08 part of Mn (NO 3) 2And sintering Liquid Additive.
In a preferred embodiment of the present invention, the composition of thermal sensitive ceramic material comprises by the mole umber: 86.2 parts of BaCO 3, 3.5 parts of SrCO 3, 4.8 parts of PbO, 5.5 parts of CaCO 3, 101.5 parts of TiO 2, 0.11 part of Y 2O 3, 0.04 part of Sb 2O 3, 0.07 part of Mn (NO 3) 2And sintering Liquid Additive.
Comprise 1～2 part of SiO by mole umber sintering Liquid Additive 2With 1.3～2 parts of Al 2O 3
In a preferred embodiment of the present invention, the sintering Liquid Additive comprises 1.1 parts of SiO 2With 1.8 parts of Al 2O 3
For solving the problems of the technologies described above, another technical solution used in the present invention is: a kind of high voltage withstanding PTC is provided, is made by thermal sensitive ceramic material.This thermal sensitive ceramic material comprises by its composition of mole umber: 86.2～87.2 parts of BaCO 3, 3.5～4.5 parts of SrCO 3, 3.8～4.8 parts of PbO, 5.5～6.5 parts of CaCO 3, 101～101.5 parts of TiO 2, 0.1～0.15 part of Y 2O 3, 0.03～0.04 part of Sb 2O 3, 0.06～0.08 part of Mn (NO 3) 2And sintering Liquid Additive.With BaCO 3, SrCO 3, PbO, TiO 2, CaCO 3Deng the principal crystalline phase composition and execute the acceptor doping thing and the sintering Liquid Additive mixes according to the ratio batching of design and makes by steps such as wet ball grinding, presintering, secondary wet process ball milling, granulation and compressing tablet, sintering, post-treatment.
Described wet ball grinding is with said mixture wet ball grinding 20～28 hours, and material: ball: the weight ratio of water is 0.5～1.5: 1～3: 1～2, and slurry is 100～150 ℃ of dryings;
Preferred wet ball grinding 24 hours, material: ball: the weight ratio of water is 1: 2: 1.5, slurry is lower dry at 130 ℃;
Described presintering is to be under 1090～1100 ℃ in temperature through the mixture behind the above-mentioned wet ball grinding, is incubated 2.5～3.5 hours;
Preferably 1090 ℃ of lower insulations 3 hours;
Described secondary wet process ball milling is that material: ball: the weight ratio of water is 0.5～1.5: 1～3 with the mixture of presintering wet ball grinding 20～28 hours again: 1～2, and slurry is 100～150 ℃ of dryings;
Preferred wet ball grinding 24 hours, material: ball: the weight ratio of water is 1: 2: 1.5, slurry is lower dry at 130 ℃;
Described granulation and compressing tablet are to add the PVA granulation, then are pressed into φ 10.32mm, thickness 3.9mm, and density is 3.3g/cm 3The disk of granulation;
Described sintering is to be under 1300～1320 ℃ in temperature, is incubated 0.5～1.5 hour, and 1.5～2 ℃/minute cool to 800 ℃, then naturally cool to room temperature;
Preferred sintering temperature is 1310 ℃, is incubated 1 hour, and 1.5 ℃/minute cool to 800 ℃;
Described post-treatment is that sintering is finished later PTC sheet printing Ag-Zn electrode, and then welding is sealed, and obtains the approximately finished product of 55 Ω of resistance.
The PTC product that thermal sensitive ceramic material of the present invention makes can pass through the described every test of background technology; can resist 4KV; the 10/700uS ripple that is struck by lightning; can be applicable to the systems such as large-scale instrument, equipment, electric power; particularly in the occasion of this class high pressure of electric power networks, large electric current, be particularly useful for the protection of telecommunication voice ply-yarn drill.
Embodiment
The below is described in detail preferred embodiment of the present invention, thereby so that advantages and features of the invention can be easier to be it will be appreciated by those skilled in the art that protection scope of the present invention is made more explicit defining.
Embodiment 1-3 is the thermal sensitive ceramic material composition:
Embodiment 1
According to the molfraction meter, with the principal crystalline phase composition of following proportioning, execute the acceptor doping thing and the sintering Liquid Additive mixes:
The principal crystalline phase composition comprises 86.2 parts of BaCO 3, 3.5 parts of SrCO 3, 4.8 parts of PbO, 5.5 parts of CaCO 3, 101 parts of TiO 2
Execute the acceptor doping thing and comprise 0.1 part of Y 2O 3, 0.03 part of Sb 2O 3, 0.06 part of Mn (NO 3) 2
The sintering Liquid Additive comprises 1 part of SiO 2With 1.3 parts of Al 2O 3
Embodiment 2
According to the molfraction meter, with the principal crystalline phase composition of following proportioning, execute the acceptor doping thing and the sintering Liquid Additive mixes:
The principal crystalline phase composition comprises 87.2 parts of BaCO 3, 4.5 parts of SrCO 3, 3.8 parts of PbO, 6.5 parts of CaCO 3, 101.5 parts of TiO 2
Execute the acceptor doping thing and comprise 0.15 part of Y 2O 3, 0.04 part of Sb 2O 3, 0.08 part of Mn (NO 3) 2
The sintering Liquid Additive comprises 2 parts of SiO 2With 2 parts of Al 2O 3
Embodiment 3
According to the molfraction meter, with the principal crystalline phase composition of following proportioning, execute the acceptor doping thing and the sintering Liquid Additive mixes:
The principal crystalline phase composition comprises 86.2 parts of BaCO 3, 3.5 parts of SrCO 3, 4.8 parts of PbO, 5.5 parts of CaCO 3, 101.5 parts of TiO 2
Execute the acceptor doping thing and comprise 0.11 part of Y 2O 3, 0.04 part of Sb 2O 3, 0.07 part of Mn (NO 3) 2
The sintering Liquid Additive comprises 1.1 parts of SiO 2With 1.8 parts of Al 2O 3
Serve as reasons PTC that this thermal sensitive ceramic material mixture makes and make the method for PTC of embodiment 4-6:
Embodiment 4
Each composition is prepared burden in embodiment 1, embodiment 2 or embodiment 3 arbitrary ratios, mix.
Wet ball grinding: mixed raw material, ball, water are made mixed slurry, wet ball grinding 20 hours with 0.5: 1: 1 weight ratio mixing;
Presintering: with above-mentioned mixed slurry after 100 ℃ of dryings, 1090 ℃ of pre-burnings 3.5 hours;
The secondary wet process ball milling: material, ball, water make mixed slurry, wet ball grinding 20 hours with 0.5: 1: 1 weight ratio mixing;
Granulation: the mixed slurry after above-mentioned the milling 100 ℃ of dryings, is then added binding agent PVA (polyvinyl alcohol) granulation;
Compressing tablet: granulated pellet is pressed into φ 10.32mm, thickness 3.9mm, density is 3.3g/cm 3The disk of granulation;
Sintering: disk 1300 ℃ of insulations 1.5 hours, is then cooled to 800 ℃ with 1.5 ℃/minute speed, naturally cool to again room temperature;
Post-treatment: printing Ag-Zn electrode after sintering is finished, then welding is sealed, and obtains the approximately finished product of 55 Ω of resistance.
Embodiment 5
Each composition is prepared burden in embodiment 1, embodiment 2 or embodiment 3 arbitrary ratios, mix.
Wet ball grinding: mixed raw material, ball, water are made mixed slurry, wet ball grinding 28 hours with 1.5: 3: 2 weight ratio mixing;
Presintering: with above-mentioned mixed slurry after 150 ℃ of dryings, 1100 ℃ of pre-burnings 2.5 hours;
The secondary wet process ball milling: material, ball, water make mixed slurry, wet ball grinding 28 hours with 1.5: 3: 2 weight ratio mixing;
Granulation: the mixed slurry after above-mentioned the milling 150 ℃ of dryings, is then added binding agent PVA (polyvinyl alcohol) granulation;
Compressing tablet: granulated pellet is pressed into φ 10.32mm, thickness 3.9mm, density is 3.3g/cm 3The disk of granulation;
Sintering: disk 1320 ℃ of insulations 0.5 hour, is then cooled to 800 ℃ with 2 ℃/minute speed, naturally cool to again room temperature;
Post-treatment: printing Ag-Zn electrode after sintering is finished, then welding is sealed, and obtains the approximately finished product of 55 Ω of resistance.
Embodiment 6
With the ratio batching of each composition in embodiment 3, mix.
Wet ball grinding: mixed raw material, ball, water are made mixed slurry, wet ball grinding 24 hours with 1: 2: 1.5 weight ratio mixing;
Presintering: with above-mentioned mixed slurry after 130 ℃ of dryings, 1090 ℃ of pre-burnings 3 hours;
The secondary wet process ball milling: material, ball, water make mixed slurry, wet ball grinding 24 hours with 1: 2: 1.5 weight ratio mixing;
Granulation: the mixed slurry after above-mentioned the milling 130 ℃ of dryings, is then added binding agent PVA (polyvinyl alcohol) granulation;
Compressing tablet: granulated pellet is pressed into φ 10.32mm, thickness 3.9mm, density is 3.3g/cm 3The disk of granulation;
Sintering: disk 1310 ℃ of insulations 1 hour, is then cooled to 800 ℃ with 1.5 ℃/minute speed, naturally cool to again room temperature;
Post-treatment: printing Ag-Zn electrode after sintering is finished, then welding is sealed, and obtains the approximately finished product of 55 Ω of resistance.
The high voltage withstanding PTC that is made by this thermal sensitive ceramic material, can pass through the described every test of background technology, can resist 4KV, the 10/700uS ripple that is struck by lightning, Practical Performance test show, the high voltage withstanding PTC that makes according to thermal sensitive ceramic material of the present invention, resistivity at room temperature is 100 Ω cm, transition temperature is 120 ℃, temperature coefficient of resistance is 20%/℃, liftdrag is 5x10 5, can satisfy all requirement on electric performance that the telecommunication voice ply-yarn drill is protected.

Claims (4)

1. a thermal sensitive ceramic material is characterized in that, it comprises following component according to the molfraction meter: 86.2 parts of BaCO 3, 3.5 parts of SrCO 3, 4.8 parts of PbO, 5.5 parts of CaCO 3, 101.5 parts of TiO 2, 0.11 part of Y 2O 3, 0.04 part of Sb 2O 3, 0.07 part of Mn (NO 3) 2And the sintering Liquid Additive, described sintering Liquid Additive comprises 1.1 parts of SiO by the mole umber 2With 1.8 parts of Al 2O 3
2. temperature sensing thermistor, it is characterized in that: described thermistor is made by thermal sensitive ceramic material claimed in claim 1.
3. a method of making the described thermistor of claim 2 is characterized in that, may further comprise the steps:
A) wet ball grinding: mixture is mixed in proportion, wet ball grinding 20～28 hours, material: ball: the weight ratio of water is 0.5～1.5: 1～3: 1～2, slurry is 100～150 ℃ of dryings;
B) presintering: be under 1090～1100 ℃ with the mixture behind the wet ball grinding in temperature, be incubated 2.5～3.5 hours;
C) secondary wet process ball milling: with the mixture of presintering wet ball grinding 20～28 hours again, material: ball: the weight ratio of water is 0.5～1.5: 1～3: 1～2, and slurry is 100～150 ℃ of dryings;
D) granulation and compressing tablet: add the PVA granulation, then be pressed into φ 10.32mm, thickness is 3.9mm, and density is 3.3g/cm 3Disk;
E) sintering: be under 1300 ℃～1320 ℃ in temperature, be incubated 0.5～1.5 hour, 1.5～2 ℃/minute cool to 800 ℃, then naturally cool to room temperature;
F) post-treatment: sintering is finished later PTC sheet printing Ag-Zn electrode, and then welding is sealed, and obtains the approximately finished product of 55 Ω of resistance.
4. according to the method for the described manufacturing thermistor of claim 3, it is characterized in that, may further comprise the steps:
A) wet ball grinding: mixture is mixed in proportion, wet ball grinding 24 hours, material: ball: the weight ratio of water is 1: 2: 1.5, and slurry is 130 ℃ of dryings;
B) presintering: be under 1090 ℃ with the mixture behind the wet ball grinding in temperature, be incubated 3 hours;
C) secondary wet process ball milling: with the mixture of presintering wet ball grinding 24 hours again, material: ball: the weight ratio of water is 1: 2: 1.5, and slurry is 130 ℃ of dryings;
D) granulation and compressing tablet: add the PVA granulation, then be pressed into φ 10.32mm, thickness is 3.9mm, and density is 3.3g/cm 3Disk;
E) sintering: be under 1310 ℃ in temperature, be incubated 1 hour, 1.5 ℃/minute cool to 800 ℃, then naturally cool to room temperature;
F) post-treatment: sintering is finished later PTC sheet printing Ag-Zn electrode, and then welding is sealed, and obtains the approximately finished product of 55 Ω of resistance.
CN 201210080495 2012-03-26 2012-03-26 Thermal sensitive ceramic material and high-voltage-resistant thermistor prepared by using thermal sensitive ceramic material and preparation method Active CN102617133B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN 201210080495 CN102617133B (en) 2012-03-26 2012-03-26 Thermal sensitive ceramic material and high-voltage-resistant thermistor prepared by using thermal sensitive ceramic material and preparation method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN 201210080495 CN102617133B (en) 2012-03-26 2012-03-26 Thermal sensitive ceramic material and high-voltage-resistant thermistor prepared by using thermal sensitive ceramic material and preparation method

Publications (2)

Publication Number Publication Date
CN102617133A CN102617133A (en) 2012-08-01
CN102617133B true CN102617133B (en) 2013-10-16

Family

ID=46557408

Family Applications (1)

Application Number Title Priority Date Filing Date
CN 201210080495 Active CN102617133B (en) 2012-03-26 2012-03-26 Thermal sensitive ceramic material and high-voltage-resistant thermistor prepared by using thermal sensitive ceramic material and preparation method

Country Status (1)

Country Link
CN (1) CN102617133B (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107010977A (en) * 2017-05-19 2017-08-04 合肥龙图腾信息技术有限公司 A kind of Resisting fractre ceramic material and preparation method thereof
CN112794640B (en) * 2021-01-05 2022-06-21 长飞光纤光缆股份有限公司 Pretreatment method of multi-component powder raw material
CN114709037A (en) * 2022-04-20 2022-07-05 深圳安培龙科技股份有限公司 Temperature-sensing PTC thermistor and preparation method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101357844A (en) * 2008-09-02 2009-02-04 周金平 PTC thermal sensitive ceramic material and method for preparing the same
CN101429020A (en) * 2008-11-26 2009-05-13 丹东国通电子元件有限公司 Method for producing positive temperature coefficient thermistor for surge suppressor
CN101492292A (en) * 2009-03-09 2009-07-29 韩城市华龙电子有限责任公司 Inorganic functional ceramic PTC thermal resistance and low-temperature production process
CN101891464A (en) * 2010-06-29 2010-11-24 章慧 High temperature thermistor and manufacturing method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101357844A (en) * 2008-09-02 2009-02-04 周金平 PTC thermal sensitive ceramic material and method for preparing the same
CN101429020A (en) * 2008-11-26 2009-05-13 丹东国通电子元件有限公司 Method for producing positive temperature coefficient thermistor for surge suppressor
CN101492292A (en) * 2009-03-09 2009-07-29 韩城市华龙电子有限责任公司 Inorganic functional ceramic PTC thermal resistance and low-temperature production process
CN101891464A (en) * 2010-06-29 2010-11-24 章慧 High temperature thermistor and manufacturing method thereof

Also Published As

Publication number Publication date
CN102617133A (en) 2012-08-01

Similar Documents

Publication Publication Date Title
CN102020463B (en) Zinc oxide piezoresistor material and preparing method thereof
CN102211924B (en) Preparation method of composite phase negative temperature coefficient thermal sensitive ceramic material
CN102617133B (en) Thermal sensitive ceramic material and high-voltage-resistant thermistor prepared by using thermal sensitive ceramic material and preparation method
CN108101366A (en) A kind of low dielectric glass pelletizing used for electronic packaging and preparation method thereof
CN105427977B (en) A kind of high-performance direct current zinc oxide resistance sheet and its preparation process
CN105272208B (en) A kind of zinc oxide varistor dielectric material and preparation method thereof
CN104616850B (en) A kind of preparation method of zinc oxide/epoxy resin composite pressure-sensitive resistance
CN103058651A (en) Modified barium titanate base unleaded positive temperature coefficient resistance material and preparing method thereof
CN105645948A (en) Preparation method of high-voltage gradient and low-leakage current pressure-sensitive resistor ceramic material
CN103880411B (en) Tindioxide piezoresistive material of rare earth modified high-gradient and preparation method thereof
CN103265284B (en) High-voltage-resistant PTC (positive temperature coefficient) ceramic and preparation method thereof
CN103360053B (en) Thermal sensitive ceramic material, PTC (positive temperature coefficient) thermistor made from thermal sensitive ceramic material for constant temperature heating and manufacturing method of PTC thermistor
CN103360052A (en) Thermal sensitive ceramic material, positive temperature coefficient (PTC) thermistor used for temperature sensing and made from thermal sensitive ceramic material and manufacturing method of thermistor
CN103910524B (en) Tin ash piezoresistive material of a kind of rare-earth oxide modified and preparation method thereof
CN101585709B (en) Preparation method of barium strontium titanate semiconductive ceramics
CN103319171A (en) Annular piezoresistor ceramic and preparation method thereof, and annular piezoresistor and preparation method thereof
CN101101811A (en) Strontium titanate pressure sensitive resistor and its production process
CN102617135A (en) Thermal sensitive ceramic material and thermistor for overcurrent protection prepared by using thermal sensitive ceramic material and preparation method
CN103553586A (en) Chromium-free, lead-free and low-voltage piezoresistor
CN103360054A (en) Thermal sensitive ceramic material, PTC (positive temperature coefficient) thermistor made from thermal sensitive ceramic material for demagnetizing colour TV and manufacturing method of PTC thermistor
CN102040378B (en) Lead-series low-resistivity heat-sensitive resistor and manufacturing method thereof
CN102745987A (en) High-curie-point lead-free PTC (Positive Temperature Coefficient) thermal sensitive ceramic material and preparation method thereof
CN102617130A (en) Heat sensitive ceramic material and thermistor with high voltage resistance
CN103360051A (en) Thermal sensitive ceramic material and positive temperature coefficient (PTC) thermistor prepared thereby, and preparation method of PTC thermistor
CN103319172B (en) Annular piezoresistor ceramic and preparation method thereof, and annular piezoresistor and preparation method thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
TR01 Transfer of patent right

Effective date of registration: 20190409

Address after: 223900 No. 5 workshop of Sihong Economic Development Zone, Suqian City, Jiangsu Province

Patentee after: Jiangsu Xinlingzhi Electronic Technology Co., Ltd.

Address before: 215500 Tonglin Road, High-tech Park, Changshu Economic Development Zone, Suzhou City, Jiangsu Province, 88

Patentee before: Changshu Linzhi Electronics Co., Ltd.

TR01 Transfer of patent right